84 マクロライドのキラル合成 : 1. Tylonolide,Protylonolide及びMycinolide全合成を目的としたMethynolideの合成
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概要
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An approach directed toward the total syntheis of 16-membered macrolides tylonolide(I), protylonolide(II) and mycinolide IV(III) has been studied. As the first phase of this study, the synthesis of methynolide(IV) was planned to attempt the construction of several chiral centers from D-glucose and the segment H and the segment J were successfully prepared as shown in scheme 3. For the construction of the segment I, D-glucose was converted to the open chain aldehyde 17 and then the α,β-unsaturated lactone 18 was obtained through Wittig-Honer reaction using trimethyl phosphonopropionate followed by the treatment with base. The lactone 18 was then converted to the glycoside 22b, which was hydrogenated successfully to the desired compound 23b as the major(24: 1) component of an epimeric mixture. Conversion of 23b to the alcohol 26 required first transformation to the olefin 25 and then hydroboration with BH_3 in CH_2Cl_2, but the isomer ratio 26: 27 was 45: 55. The alternative synthesis of 26 is currently being investigated. The segments B, the left parts of protylonolide and tylonolide were synthesized based on a satisfactory result in the preparation of H, and J. The acetonide 54 derived from 3 was converted to the aldehyde 55, which was then transformed successfully through Wittig reaction to the α,β-unsaturated ester 56. Finally, the alcohol 50 efficiently derived from 3 was transformed to the benzoate 57 in which the hydroxyl group was blocked as an benzylidene derivative(57→58, 67.8%) using the method recently developped by us. Treatment of the aldehyde 59 with Wittig reagent led to the unsaturated ester 60 in good yield.
- 天然有機化合物討論会の論文
- 1981-09-10
著者
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及川 裕二
Faculty Of Pharmaceutical Sciences Hokkaido University
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及川 裕二
北大薬
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米光 宰
北大薬
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米光 宰
北海道大学薬学部
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米光 宰
北大 薬
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